CN110876817B

CN110876817B - Porous PEEK (polyetheretherketone) bionic bone repair material, PEEK bionic bone part with multilayer structure and preparation method thereof

Info

Publication number: CN110876817B
Application number: CN201910779682.3A
Authority: CN
Inventors: 李凝; 陈德强; 胡礼广; 林祝亮; 刘露; 李新辉
Original assignee: Zhejiang Normal University CJNU
Current assignee: Zhejiang Normal University CJNU
Priority date: 2019-08-22
Filing date: 2019-08-22
Publication date: 2022-03-04
Anticipated expiration: 2039-08-22
Also published as: CN110876817A

Abstract

The invention discloses a porous PEEK biomimetic bone repair material, a PEEK biomimetic bone product with a multi-layer structure and a preparation method thereof. In parts by mass, the raw material composition of the porous PEEK biomimetic bone repair material includes 100 parts of base material, 12-16 parts of reinforcing material, 0.1-3 parts of foaming agent and 0.1-0.5 part of biological active substance; the base material includes mass ratio 14:1 PEEK powder and PTFE powder. In the PEEK biomimetic bone repair material of the present invention, a foaming agent is used to form pores in the matrix material, which is different from the pore-forming mechanism of the porogen, and the foaming agent does not need to be removed after the pores are formed, which simplifies the process and saves energy. In addition, the addition of bioactive substances will effectively improve the biocompatibility of biomimetic materials with human tissues, improve the physiological activity of the human body's own original body fluid, and help stimulate the survival of cells, tissues and neurons in the bionic body and improve repair performance.

Description

Porous PEEK (polyetheretherketone) bionic bone repair material, PEEK bionic bone part with multilayer structure and preparation method thereof

Technical Field

The invention belongs to the field of bionic bone materials, and particularly relates to a porous PEEK bionic bone repair material, a PEEK bionic bone part with a multilayer structure and a preparation method thereof.

Background

The repair of massive bone defects caused by factors such as trauma, infection, tumor excision and the like is a difficult problem faced by clinical medicine at home and abroad for a long time, and the repair materials of the massive bone defects mainly come from autogenous bone, artificial bone, organic glass, bone cement, silicon rubber, stainless steel, titanium mesh, polyether ether ketone (PEEK) and the like. Wherein, autologous bone sources are limited, and patients may need to suffer additional pain in order to obtain autologous bone; other bone repair materials not only easily cause potential infection, immunological rejection and other problems, but also can only play a part of the function replacement role.

PEEK is currently the repair material with a modulus of elasticity closest to that of human bone and is therefore the focus of current skull repair research. PEEK has characteristics such as good biocompatibility, excellent mechanical properties, light weight, and X-ray penetrability, and although PEEK itself has a defect of poor osseointegration, the osseointegration ability of PEEK can be moderately improved by attaching bioactive substances such as nano-hydroxyapatite, nano-titanium dioxide, calcium silicate, β -tricalcium phosphate, and bioactive glass to the surface of PEEK.

For example, the Chinese patent application with publication number CN108273137A discloses a porous bionic skull repairing material and a personalized manufacturing method, the porous bionic skull repairing material is matched with a human skull structure, the surface layer is a compact layer, the inner layer is a loose layer, the compact layer is bionic cortical bone, and the loose layer is a bionic skull trabecular structure. The porous bionic skull repairing material can be made into a porous bionic skull repairing prosthesis by adopting a mixed molding method, and the mixed molding method comprises the following steps: (1) scanning the skull of a patient by using a computed tomography technology, segmenting and extracting data by using image processing software, reconstructing a three-dimensional model of the skull and a defect part of the patient, and calculating the size and the curvature of the artificial skull of the defect part;

(2) Preparing a composite structure plate: firstly, mixed powder is prepared: adding polyaryletherketone materials, bioactive substances and pore-forming agents into a V-shaped mixer according to a certain proportion, and fully and uniformly mixing to respectively prepare powder materials of a compact layer and a loose layer; cold press molding: preparing mixed powder of a compact layer and a loose layer according to the ideal volume of a 102% mold: placing the powder of the dense layer and the powder of the loose layer prepared in the step I into a mould, placing the mould into a hydraulic press, compacting the materials at the pressure of 1-150MPa to prepare a plate, repeatedly pressurizing and releasing pressure for one or more times to completely discharge residual gas in the mould, maintaining the pressure for 1-60min, and ensuring the quality and the performance of the plate; melting: opening an external heating device for the pressed blank or the die obtained in the step two or putting the pressed blank or the die into a high-temperature oven, and melting and heating the plate, wherein the heating temperature is set to be between the melting point of the polyaryletherketone material and the melting point of the pore-forming agent; fourthly, hot-press forming: rapidly placing the melted blank obtained in the step (III) or placing the blank in a press, repeatedly pressurizing and releasing pressure once or for many times under the maximum pressure of 1-100MPa, maintaining the pressure for 10-60min, cooling the die at the speed of 40 ℃/min, placing the die into a demolding seat, demolding and taking out the blank;

(3) Shaping treatment: guiding the established three-dimensional model of the skull defect part of the patient into a die-free multipoint forming device, heating the blank obtained in the step (2) to a temperature between the plastic deformation temperature and the melting point temperature of the polyaryletherketone material, quickly moving the blank to the die-free multipoint forming device, performing compression forming to obtain a personalized skull repairing material customized according to the patient, and cutting the personalized skull repairing material into artificial skull with the size exceeding the calculated size by about 1 cm;

(4) preparing a skull repairing prosthesis with a porous bionic composite structure: and (4) placing the personalized skull repairing prosthesis obtained in the step (3) in an ultrasonic water bath kettle, a constant temperature oscillator or a salt bath kettle, setting the temperature to be 50-100 ℃, completely separating out a pore-forming agent, and then carrying out drying treatment (for about 24 hours) to obtain the porous bionic skull repairing prosthesis customized according to the patient.

The porous bionic skull repairing material has the following defects: the pore-foaming agent adopted in the preparation process is conventional inorganic salt, and the pore-foaming agent needs to be completely separated out and dried after compression molding, so that the time consumption is long and the energy consumption is large.

Disclosure of Invention

The invention aims to provide a porous PEEK bionic bone repair material, a PEEK bionic bone part with a multilayer structure and a preparation method thereof.

In order to achieve the above purpose, the technical solution of the present application is as follows:

a porous PEEK bionic bone repair material comprises, by mass, 100 parts of a base material, 12-16 parts of a reinforcing material, 0.1-3 parts of a foaming agent and 0.1-0.5 part of a bioactive substance;

the base material comprises PEEK powder and PTFE powder in a mass ratio of 14: 1.

According to the PEEK bionic bone repair material, the foaming agent is adopted to form pores in the base material, the pore-forming mechanism is different from that of a pore-forming agent, and the foaming agent does not need to be removed after the pores are formed, so that the process is simplified, and the energy is saved.

The addition of the bioactive substances can effectively improve the biocompatibility of the bionic material and human tissues, improve the physiological activity of the human body original body fluid, and is beneficial to exciting the survival degree of cells, tissues and neurons in the bionic body and improving the repair performance.

In the porous PEEK bionic bone repair material, the foaming agent is sodium bicarbonate and azodicarbonamide (namely foaming agent AC) in a mass ratio of 9: 1.

In the porous PEEK bionic bone repair material, the reinforcing material comprises silk fibroin modified nano-hydroxyapatite and sulfonated PEEK modified calcium carbonate whisker in a mass ratio of 3: 7.

The natural polymer silk fibroin has unique mechanical property, excellent biocompatibility, excellent moisture absorption and preservation and antimicrobial capability, and wide source, and the modification of the nano hydroxyapatite by utilizing the silk fibroin is expected to overcome the problem of insufficient mechanical property of pure hydroxyapatite, and is suitable for the repair and replacement of hard tissues, particularly loaded bones.

And the sulfonated PEEK is adopted to modify the surface of the calcium carbonate whisker, so that the aim of enhancing the compatibility between the surface of the calcium carbonate whisker and an organic material interface can be achieved, and the requirement on the mechanical property of the bionic material in a human body can be further met.

In the porous PEEK bionic bone repair material, the silk fibroin modified nano hydroxyapatite is obtained by soaking the nano hydroxyapatite in a silk fibroin solution with the concentration of 3% for 20-40 min;

the sulfonated PEEK modified calcium carbonate whisker is obtained by mixing and crosslinking calcium carbonate whisker and sulfonated PEEK in a mass ratio of 100:3, and the sulfonation degree of the sulfonated PEEK is 84.0-99.6%.

In the porous PEEK bionic bone repair material, the bioactive substances are as follows: serum containing 0.125% concentration of induction stock and plasma containing 1.8% concentration of mesenchymal stem cells;

The concentration of the inducing stock solution in serum is 0.12-0.14%, and the concentration of mesenchymal cells in plasma is 1.6-2.0%.

In the PEEK bionic bone part with the multilayer structure, each layer of structure is made of the porous PEEK bionic bone repair material, and the content of the foaming agent in the raw material composition of each layer of structure is gradually increased from the outer side to the center of the PEEK bionic bone part. The higher the content of foaming agent, the higher the porosity, so that the produced bionic bone is consistent with the human bone structure.

The porous PEEK bionic bone repair material can be prepared into various shapes of bionic bone parts and used for repairing bone structures of various parts of a human body.

As a specific embodiment, the PEEK bionic bone part with a multilayer structure of the invention is a human tibia bionic part, which sequentially comprises a periosteum layer, a compact bone layer, a loose bone layer and a medullary cavity from outside to inside, wherein the thickness of the periosteum layer is 0.2mm, the porosity of the compact bone layer is 10-15%, the porosity of the loose bone layer is 36-44%, and the diameter of the medullary cavity is 6-12 mm.

The raw materials of the periosteum layer comprise 100 parts of base material, 12-16 parts of reinforcing material, 0.1 part of foaming agent and 0.1-0.3 part of bioactive substance by weight;

The raw material composition of the bone dense layer comprises 100 parts of base material, 12-16 parts of reinforcing material, 0.5 part of foaming agent and 0.3-0.5 part of bioactive substance;

the raw material composition of the bone loose layer comprises 100 parts of matrix material, 12-16 parts of reinforcing material, 3 parts of foaming agent and 0.3-0.5 part of bioactive substance.

The preparation method of the PEEK bionic bone part with the multilayer structure comprises the following steps:

(1) adding PTFE powder and a reinforcing material into PEEK powder according to preset raw material composition, continuously stirring for 24 hours, adding a foaming agent, and continuously stirring for 1-2 hours to respectively obtain a periosteum layer raw material mixture, a compact bone layer raw material mixture and a bone loose layer raw material mixture;

(2) prefabricating a shin bone mold, preheating to 220 ℃, respectively adding the periosteum layer raw material mixture, the compact bone layer raw material mixture and the bone loose layer raw material mixture into corresponding mold cavities, then heating to 340-;

(3) placing the workpiece into a container at the temperature of 110-;

(4) putting the workpiece into flowing clear water for washing for 6-10h, taking out and drying;

(5) soaking the workpiece in serum containing an induction stock solution for 12h, taking out and drying;

(6) And (3) putting the part into plasma containing mesenchymal stem cells to be soaked for 2h to obtain the PEEK bionic bone part with the multilayer structure.

The invention also provides application of the PEEK bionic bone part with the multilayer structure in bone repair.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the PEEK bionic bone repair material, the foaming agent is adopted to form pores in the base material, the pore-forming mechanism is different from that of a pore-forming agent, and the foaming agent does not need to be removed after the pores are formed, so that the process is simplified, and the energy is saved.

(2) The addition of the bioactive substances can effectively improve the biocompatibility of the bionic material and human tissues, improve the physiological activity of the human body original body fluid, and is beneficial to exciting the survival degree of cells, tissues and neurons in the bionic body and improving the repair performance.

Drawings

FIG. 1 is a schematic structural diagram of a PEEK bionic bone part with a multilayer structure according to the present invention;

FIG. 2a is an electron microscope microscopic view of the periosteum layer of a PEEK biomimetic bone product with a multi-layer structure according to the present invention;

FIG. 2b is an electron microscope microscopic view of the dense bone layer of a PEEK biomimetic bone product with a multi-layer structure according to the present invention;

FIG. 2c is an electron microscope microscopic view of the bone cancellous layer of a PEEK biomimetic bone product with a multi-layered structure according to the present invention.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and the detailed description.

Example 1

The PEEK bionic bone part with the multilayer structure of the embodiment is a human tibia bionic part, and the structure of the PEEK bionic bone part is shown in fig. 1, and the PEEK bionic bone part sequentially comprises a periosteum layer 1, a bone dense layer 2, a bone loose layer 3 and a bone marrow cavity 4 from outside to inside, and is consistent with the structure of a human tibia.

The preparation method comprises the following steps:

(1) putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 3.6g of calcium carbonate whiskers and 0.108g of sulfonated PEEK (the sulfonation degree is 84%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 1.5g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.03g of sodium bicarbonate and 0.003g of azodicarbonamide, and continuously stirring for 30min to obtain an periosteum raw material mixture;

putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 3.6g of calcium carbonate whiskers and 0.108g of sulfonated PEEK (the sulfonation degree is 84%) into the PEEK powder, continuously stirring for 24h, adding 1.5g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.09g of sodium bicarbonate and 0.01g of azodicarbonamide, and continuously stirring for 30min to obtain a raw material mixture of a compact bone layer;

28g of PEEK powder and 2g of PTFE powder are placed in a container, 3.6g of calcium carbonate whiskers and 0.108g of sulfonated PEEK (the sulfonation degree is 84%) are added into the PEEK powder, the mixture is continuously stirred for 24 hours, then 1.5g of silk fibroin modified hydroxyapatite is added, the mixture is continuously stirred for 12 hours, then 0.9g of sodium bicarbonate and 0.02g of azodicarbonamide are added, and the mixture is continuously stirred for 30 minutes to obtain a raw material mixture of a bone loose layer;

the silk fibroin modified hydroxyapatite is obtained by the following method: soaking nanometer hydroxyapatite in 3% silk fibroin solution for 30min, filtering, and oven drying at 80 deg.C.

(2) Respectively adding the periosteum layer raw material mixture, the compact bone layer raw material mixture and the bone loose layer raw material mixture into corresponding cavities of a 340-DEG C hot-pressing die, reacting for 15min under 25MPa, cooling the die to 160 ℃ by water, opening the die, and taking out a finished piece;

(3) putting the workpiece into a furnace, keeping the temperature at 110 ℃ for 10h, taking out the workpiece, and cooling the workpiece to room temperature;

(4) putting the workpiece into flowing clear water for washing for 6h, taking out and drying;

(5) putting the workpiece into a serum solution for soaking for 12 hours, taking out and drying;

(6) the member was immersed in a plasma solution containing hematopoietic stem cells for 2 hours to obtain a PEEK bionic bone member having a multilayer structure of the present example.

Example 2

The PEEK bionic bone part with the multilayer structure is a human tibia bionic part, and the structure of the PEEK bionic bone part is shown in fig. 1, and the PEEK bionic bone part sequentially comprises a periosteum layer, a bone dense layer, a bone loose layer and a bone marrow cavity from outside to inside and is consistent with the structure of a human tibia.

The preparation method comprises the following steps:

(1) putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.0g of calcium carbonate whiskers and 0.12g of sulfonated PEEK (the sulfonation degree is 90%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.0g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.03g of sodium bicarbonate and 0.003g of azodicarbonamide, and continuously stirring for 30min to obtain a raw material mixture of the periosteum layer;

putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.0g of calcium carbonate whiskers and 0.12g of sulfonated PEEK (the sulfonation degree is 90%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.0g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.09g of sodium bicarbonate and 0.01g of azodicarbonamide, and continuously stirring for 30min to obtain a bone compact layer raw material mixture;

putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.0g of calcium carbonate whiskers and 0.12g of sulfonated PEEK (the sulfonation degree is 90%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.0g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.9g of sodium bicarbonate and 0.02g of azodicarbonamide, and continuously stirring for 30min to obtain a bone loose layer raw material mixture;

(2) Respectively adding the periosteum layer raw material mixture, the compact bone layer raw material mixture and the bone loose layer raw material mixture into corresponding cavities of a 350-DEG C hot-pressing die, reacting for 15min under 30MPa, cooling the die to 170 ℃ by water, opening the die, and taking out a finished piece;

(3) putting the workpiece into a furnace, keeping the temperature at 110 ℃ for 12h, taking out the workpiece, and cooling the workpiece to room temperature;

(4) putting the workpiece into flowing clear water for washing for 8 hours, taking out and drying;

Example 3

The preparation method comprises the following steps:

(1) putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.8g of calcium carbonate whiskers and 0.144g of sulfonated PEEK (the sulfonation degree is 99.6%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.4g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.03g of sodium bicarbonate and 0.003g of azodicarbonamide, and continuously stirring for 30min to obtain an periosteum raw material mixture;

Putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.8g of calcium carbonate whiskers and 0.144g of sulfonated PEEK (the sulfonation degree is 99.6%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.4g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.09g of sodium bicarbonate and 0.01g of azodicarbonamide, and continuously stirring for 30min to obtain a raw material mixture of the compact bone layer;

putting 28g of PEEK powder and 2g of PTFE powder into a container, adding 4.8g of calcium carbonate whiskers and 0.144g of sulfonated PEEK (the sulfonation degree is 99.6%) into the PEEK and PTFE powder, continuously stirring for 24h, adding 2.4g of silk fibroin modified hydroxyapatite, continuously stirring for 12h, adding 0.9g of sodium bicarbonate and 0.02g of azodicarbonamide, and continuously stirring for 30min to obtain a bone pine layer raw material mixture;

(2) Respectively adding the periosteum layer raw material mixture, the compact bone layer raw material mixture and the bone loose layer raw material mixture into corresponding cavities of a 360-DEG C hot-pressing die, reacting for 10min under 45MPa, cooling the die to 180℃ by water, opening the die, and taking out a finished piece;

(3) Putting the workpiece into a furnace, keeping the temperature at 110 ℃ for 14h, taking out the workpiece, and cooling the workpiece to room temperature;

(4) putting the workpiece into flowing clear water for washing for 10 hours, taking out and drying;

The slices of the human tibial bionic parts prepared in the embodiments 1 to 3 are taken and observed under an electron microscope, wherein the observation results of the slices of the human tibial bionic part in the embodiment 1 are shown in fig. 2a, fig. 2b and fig. 2 c.

As can be seen from fig. 2a, the periosteum layer with the foaming agent content of 0.1% has relatively low porosity and relatively small pore diameter, the section also presents a smooth spherical bubble structure, the compactness of the matrix is high, and the gaps basically present a discontinuous spatial structure; as can be seen from fig. 2b, the porosity of the compact bone layer with 0.5% of foaming agent relative to the periosteum material is increased (the porosity of the compact bone layer is 10-15%), the pore diameter is also increased, the connectivity among the pores begins to appear, and the three-dimensional communication structure between the layers is more obvious; as can be seen from FIG. 2c, the spongy layer material with a foaming agent content of 3% has the largest pore size and larger porosity (the porosity of the spongy layer is 36-44%), and the cells are effectively communicated with each other, and meanwhile, irregular overlapping of the large pores and the small pores appears, and the spongy layer material shows consistency with the solid bone structure.

The human tibia bionic workpiece prepared in the embodiment 1-3 is taken, and the Poisson's ratio (namely, transverse deformation coefficient) of the material is detected on a ZWICK Z050 material biaxial mechanical property testing machine, wherein the test conditions are as follows: room temperature, design cuboid style size: 15mm multiplied by 10mm, displacement control is adopted for loading, the loading rate is set to be 0.2mm/min, the compressive strain and the axial strain when the compression is carried out for 2min are measured, and then the Poisson ratio is calculated. The results are shown in Table 1.

TABLE 1 Poisson ratio test results (compression) of human tibial biomimetic fabricated parts prepared in examples

	Example 1	Example 2	Example 3
				Poisson's ratio	0.328	0.358	0.376

The human tibial bionic parts prepared in the embodiments 1 to 3 are taken, and the volume abrasion loss and the friction coefficient of each part are detected. The friction wear test is carried out on an MM-200 type wear testing machine (Jinan), an open boundary lubrication wear mode is adopted, the deproteinized calf serum injection is lubricated, the dropping amount is 20 drops/min, an upper test sample (a sample for the test) is in reciprocating horizontal movement, the movement frequency is 16 times/min, and the displacement is 1 MM; the rotational speed of the lower sample (bone material) was 200 rad/min.

The wear resistance of the sample is measured by the volume wear loss, the width of the grinding mark is measured by a 10-time reading microscope, each grinding mark is measured for 5 times, and the width of the grinding mark is obtained by averaging. The volumetric wear amount was calculated by the following formula:

In the formula: v represents the wear volume, B represents the width of the lower sample of 10mm, B represents the width of the wear scar, and r represents the radius of the lower sample of 20 mm.

The friction torque of the friction pair was measured using a friction torque scale of 1000N · mm, and the friction coefficient was calculated by the following formula:

in the formula: μ represents the coefficient of friction, T represents the friction torque (N · m), R represents the lower specimen radius of 0.02m, and P represents the vertical load (N) to which the specimen is subjected.

The results are shown in Table 2.

TABLE 2 results of measurements of volume wear and friction coefficient of bionic human tibia parts in each example

	Example 1	Example 2	Example 3
				Volume wear amount	0.0018g/day	0.0013g/day	0.0007g/day
Coefficient of friction	0.123	0.114	0.086

Comparative example 1

The PEEK bionic bone part with a multilayer structure in this embodiment has the same manufacturing method as that in embodiment 1, but the foaming agent adopted in the raw materials of the bone loose layer is: 0.09g of sodium bicarbonate and 0.018g of azodicarbonamide.

Comparative example 2

The PEEK bionic bone part with a multilayer structure in this embodiment has the same manufacturing method as that in embodiment 1, but the foaming agent adopted in the raw materials of the bone loose layer is: 0.05g of sodium bicarbonate and 0.05g of azodicarbonamide.

Comparative example 3

The PEEK bionic bone part with a multilayer structure in this embodiment has the same manufacturing method as that in embodiment 1, but the foaming agent adopted in the raw materials of the bone loose layer is: 0.01g of sodium bicarbonate and 0.09g of azodicarbonamide.

Comparative example 4

The PEEK bionic bone part with a multilayer structure in this embodiment has the same manufacturing method as that in embodiment 1, but the foaming agent adopted in the raw materials of the bone loose layer is: 0.1g sodium bicarbonate.

Comparative example 5

The PEEK bionic bone part with a multilayer structure in this embodiment has the same manufacturing method as that in embodiment 1, but the foaming agent adopted in the raw materials of the bone loose layer is: 0.1g azodicarbonamide.

The average porosity of the bone cancellous layer of the PEEK simulated bone parts obtained in example 1 and comparative examples 1 to 5 was measured, and the results are shown in table 3.

TABLE 3

Examples	Foaming agent	Average porosity
			Example 1	Sodium bicarbonate and azodicarbonamide 45:1	40％
Comparative example 1	Sodium bicarbonate and azodicarbonamide 5:1	25％
			Comparative example 2	Sodium bicarbonate and azodicarbonamide 1:1	12％
Comparative example 3	Sodium bicarbonate and azodicarbonamide 1:9	9％
			Comparative example 4	Sodium bicarbonate alone	18％
Comparative example 5	Azodicarbonamide only	11％

Claims

1. a porous PEEK biomimetic bone repair material, is characterized in that, in parts by mass, the raw material composition comprises 100 parts of matrix materials, 12-16 parts of reinforcing materials, 0.1-3 parts of foaming agents and 0.1-0.5 parts of bioactive substances share;

The base material includes medical PEEK powder and medical PTFE powder with a mass ratio of 14:1;

The reinforcing material includes silk fibroin-modified nano-hydroxyapatite and sulfonated PEEK-modified calcium carbonate whiskers;

The porous PEEK bionic bone repair material is prepared by the following method:

(1) According to the preset raw material composition, add PTFE powder and reinforcing material to PEEK powder, add foaming agent after continuous stirring for 24 hours, and continue stirring for 1-2 hours to obtain a raw material mixture;

(2) Pre-fabricate a human tibia mold and preheat to 220°C, add the raw material mixture into the corresponding mold cavity, then heat up to 340-360°C, react under 25-40MPa hot pressing for 10-15min, and cool the mold to 160°C Open the mold at -180℃ and take out the part;

(3) Put the product into the temperature of 110-130℃ for 10-14h, take it out and cool it to room temperature;

(4) Put the parts into flowing clean water to rinse for 6-10h, take them out and dry them;

(5) Put the part into the serum containing the induction stock solution and soak it for 12h, take it out and dry it;

(6) Soak the product in plasma containing mesenchymal stem cells for 2 hours to obtain the porous PEEK biomimetic bone repair material.

2. The porous PEEK bionic bone repair material according to claim 1, wherein the foaming agent is sodium bicarbonate and azodicarbonamide in a mass ratio of 9:1.

3. The porous PEEK biomimetic bone repair material according to claim 1, wherein the reinforcing material comprises silk fibroin-modified nano-hydroxyapatite and sulfonated PEEK modified in a mass ratio of 3:7 of calcium carbonate whiskers.

4. The porous PEEK biomimetic bone repair material according to claim 3, wherein the silk fibroin-modified nano-hydroxyapatite is prepared by soaking the nano-hydroxyapatite in silk fibroin with a concentration of 3%. Obtained after 20-40min in protein solution;

The sulfonated PEEK-modified calcium carbonate whiskers are obtained by mixing calcium carbonate whiskers with a mass ratio of 100:3 and sulfonated PEEK and then cross-linking, and the sulfonation degree of the sulfonated PEEK is 84.0-99.6%.

5. The porous PEEK biomimetic bone repair material according to claim 1, wherein the biologically active substances are: serum containing induced stock solution and plasma containing mesenchymal stem cells;

The concentration of the induced stock solution in serum was 0.12-0.14%, and the concentration of mesenchymal stem cells in plasma was 1.6-2.0%.

6. A PEEK biomimetic bone product with a multi-layer structure is characterized in that, each layer structure is made of the porous PEEK biomimetic bone repair material described in any one of claims 1-5, and is made from PEEK biomimetic bone. From the outer side of the part to the center, the content of the foaming agent in the raw material composition of each layer structure gradually increases.

7. The PEEK biomimetic bone part with a multi-layer structure as claimed in claim 6, characterized in that it is a human tibia biomimetic part, and the human tibia biomimetic part sequentially comprises a periosteum layer (1), a bone density from outside to inside The stromal layer (2), the cancellous bone layer (3) and the bone marrow cavity (4), the thickness of the periosteum layer (1) is 0.2 mm, and the porosity of the cortical bone layer (2) is 10-10 mm. 15%, the porosity of the cancellous bone layer (3) is 45-60%, and the diameter of the bone marrow cavity (4) is 6-12 mm.

8. The PEEK biomimetic bone part with a multi-layer structure according to claim 7, characterized in that, in parts by mass, the raw material composition of the periosteum layer (1) comprises 100 parts of a matrix material, 12 parts of a reinforcing material -16 parts, 0.1 part of foaming agent and 0.1-0.3 part of biological active substance;

The raw material composition of the compact bone layer (2) includes 100 parts of base material, 12-16 parts of reinforcing material, 0.5 part of foaming agent and 0.3-0.5 part of biological active substance;

The raw material composition of the cancellous bone layer (3) includes 100 parts of matrix material, 12-16 parts of reinforcing material, 3 parts of foaming agent and 0.3-0.5 part of biological active substance.

9. the preparation method of the PEEK biomimetic bone product with multilayer structure as described in any one of claim 6-8, is characterized in that, comprises the following steps:

(1) According to the preset raw material composition, add PTFE powder and reinforcing material to PEEK powder, add foaming agent after continuous stirring for 24 hours, and continue stirring for 1-2 hours to obtain the periosteal layer raw material mixture and the bone compact layer raw material mixture respectively. and cancellous layer raw material mixture;

(2) Prefabricating a human tibia mold and preheating to 220°C, adding the periosteal layer raw material mixture, the compact bone layer raw material mixture and the cancellous bone layer raw material mixture to the corresponding mold cavity, and then heating to 340-360°C, React under 25-40MPa hot pressure for 10-15min, cool the mold to 160-180℃, open the mold, and take out the part;

(4) Put the parts into flowing clean water for 6-10 hours, take them out and dry them;

(6) Soak the product in plasma containing mesenchymal stem cells for 2 hours to obtain the PEEK biomimetic bone product with a multi-layer structure.